N-nitroso-n-phosphonomethyl glycine compounds and herbicidal use thereof

ABSTRACT

N-Nitroso-N-phosphonomethylglycine compounds have been produced by the reaction of an inorganic nitrite and Nphosphonomethylglycine. These compounds are useful as postemergent herbicides.

United States Patent Alt June 10, 1975 [541 ggigrggg FOREIGN PATENTS ORAPPLICATIONS USE THEREOF 2,152,826 9/1972 Germany 260/5025 [75]Inventor: Gerhard 1-]. Alt, Creve Coeur, M0.

Primary Examiner-Howard T. Mars [73] Asslgnee: Monsanto Company, St.LOUIS, Mo. Asst-3mm Examiner Nicky Chan [22] Filed: Sept. 4, 1973Attorney, Agent, or Firm-William T. Black; Donald W. Peterson [2|] Appl.No.: 394,019

In. s N Nitroso N h -p osphonomethylglycme compounds [58] Field Seal-chm260/5025 have been produced by the reaction of an inorganic I nitriteand N-phosphonomethylglycine. These com- Reierences cued pounds areuseful as postemergent herbicides.

UNITED STATES PATENTS 12/1964 Toy et al 260/268 4 Claims, No Drawings 1N-NlTROSO-N-PHOSPHONOMETHYL GLYCINE COMPOUNDS AND HERBICIDAL USE THEREOFThis invention relates to N-nitroso-N-phosphonomethylglycine compounds,the preparation thereof, and their use as herbicides and in herbicidalcompositions.

wherein M, M, and M are each individually hydrogen or a saltformingcation selected from the group consisting of alkali metals, alkalineearth metals, ammonium, aliphatic ammonium and phenyl ammonium with theproviso that at least one of M, M, or M is H when the others areammonium, aliphatic ammonium or phenyl ammonium.

The term alkali-metal encompasses lithium, sodium, potassium, cesium andrubidium; and the term alkaline earth metal includes beryllium,magnesium calcium, strontium and barium.

The term aliphatic ammonium" as employed herein encompasses mono-, diandtri-alkyl ammonium groups wherein the alkyl groups contain from 1 to 6carbon atoms as well as the cycloalkyl groups containing from 3 to 6carbon atoms. The term phenyl ammonium" as employed herein encompassesaniline and substituted anilines such as the mono-, diand tri-halo,nitro, methoxy, methyl, and ethyl anilines.

The aliphatic ammonium group includes, for example, mono-, diandtri-methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, t-butyl,t-pentyl ammonium groups as well as cyclopropyl ammonium,cyclobutylethylammonium, cyclopentylmethyl ammonium, cyclohexylammoniumand the like.

Illustrative of the phenyl ammonium group are those derived from theprimary phenyl amines such as aniline, methoxyaniline, ethoxyaniline,o,m,p-toluidine, o,m,p-chloroaniline, o,m,p-anisidine, o,m, andpnitroaniline, 2,4-dichloroaniline, 3,5-dichloroaniline,2,5-diiodoani1ine, o,m, and p-bromoaniline and the like.

The compounds of the instant invention are produced by the reaction ofN-phosphonomethylglycine with a nitrite salt in an aqueous media. Forexample, the monosodium salt of N-nitroso-N-phosphonomethylglycine isproduced by reacting approximately equal molar quantities of sodiumnitrite with N-phosphonomethylglycine. The free acid can then beprepared by acidification of the acid mixture with an acid such ashydrochloric acid. The ammonium and other salts can then be produced byneutralization with the appropriate base or by reacting the salt withammonium chloride or an amine hydrochloride salt.

Nitrites which can be employed in this process include the alkali metaland alkaline earth metal nitrites.

In conducting the process of the instant invention, the ratio of thealkali metal nitrite to the N-phosphonomethylglycine is not narrowlycritical and can be varied over a wide range, i.e., from about 1 to 10to 1 0 to 1. Of course, it is preferred to employ the alkali metalnitrite and the N-phosphonomethyl glycine in ap- 2 proximately equimolaramounts, i.e., molar ratio of about l.05l to 1-1.05 in as much as alarge excess of one over the other renders the separation of the productmore difficult.

The temperature at which the process is conducted can vary from about 0to C. It is preferred for convenience to conduct the process at atemperature of from about 5 to about 30C.

The process of the instant invention is preferably conducted in anaqueous medium so the inorganic nitrite and N-phosphonomethylglycine arecontacted in solution.

The compounds and compositions of the present invention find use asherbicides and phytotoxicants.

The following examples serve to further illustrate the invention. Allparts are parts by weight unless otherwise expressly set forth.

EXAMPLE 1 N-phosphonomethylglycine (0.02 moles) was suspended in water(20 ml.) in a glass reactor. Sodium nitrite (0.02 moles) dissolved inwater (10 ml.) was added dropwise with stirring. The reaction mixturewas stirred at room temperature for 3 hours and then anilinehydrochloride (0.02 moles) in water was added. A small amount of ethanol(approximately 7 cc) was added and a solid crystallized. The solid wasremoved by filtration, yielding 2.1 gms. of a material (m.p. 173-l75C.with decomposition) identified as N- nitroso-N-phosphonomethylglycineaniline salt by nuclear magnetic resonance spectral analysis.

EXAMPLE 2 N-Phosphonomethylglycine (16.9 g., 0.1 mole) was suspended inwater (40 ml.) in a glass reactor and sodium nitrite (7.0 g., 0.1 mole)dissolved in water (20 ml.) was added dropwise with stirring. Thereaction mixture was stirred until homogenous, allowed to standovernight. The reaction mixture was filtered and washed into a ml. flaskto give a 1 molar aqueous solution of the monosodium salt ofN-nitroso-N-phosphonomethylglycine.

EXAMPLE 3 The post-emergent herbicidal activity of various compounds ofthis invention is demonstrated as follows. The active ingredients areapplied in spray form to 21-day old specimens of various plant species.The spray, a water solution containing the active ingredient and asurfactant (1 percent by weight), is applied to the plants in differentsets of pans at several rates (pounds per acre) of active ingredient.The treated plants are placed in a greenhouse and the effects observedafter approximately 4 weeks. The results are shown in Table Thepost-emergence herbicidal activity index used in Table l is as follows:

Lu u-O The plant species utilized in these tests are identified byletter in accordance with the following legend:

A Canada Thistle G Morningglory B Nutsedge H Lambsquarters C Ouackgrassl Smartweed D .lohnsongrass J Downy bromc E Cocklebur K Barnyardgrass FVelvellcaf TABLE I Compound of Example I Rate Ih/acre A B C D E F G H lJ K A: (J I 0 I l I l I 0 2 f4 1 0 l 0 2 I 2 2 0 I 2 A 2 I 2 I 2 2 2 4 Il 2 U] 2 2 3 2 2 2 2 3 2 I 3 4 4 I 3 I 2 2 2 4 4 2 4 l0 4 2 4 2 2 2 2 4I 4 4 Compound of Example ll 4 I 0 0 0 I 0 I 0 0 0 I Other compoundsincluded within the scope of this invention which can be produced by themethods set forth in the preceding examples are, for example:

Disodium salt of N-nitroso-N-phosphonomethylglycine Monopotassium saltof N-nitroso-N-phosphonomethylglycine Dipotassium salt ofN-nitroso-N-phosphonomethylglycine Tripotassium salt ofN-nitroso-N-phosphonomethylglycine Trisodium salt ofN-nitroso-N-phosphonomethylglycine Monomethylamine salt ofN-nitroso-N-phosphonomethylglycine l lonodiisopropylamine salt ofN-nitroso-N-phosphonomethylglycine Monodiethanolamine salt ofN-nitroso-N-phosphonomethylglycine Hemicalcium salt ofN-nitroso-N-phosphonomethvlglycine Calcium salt ofN-nitroso'N-phosphonomethylglycine Hemimagnesium salt ofN-nitroso-N-phosphonomethylglycine Magnesium salt ofN-nitr0so-N-phosphonomethylglycine Hemicopper salt ofN-nitroso-N-phosphonomethylglycine Monolithium salt ofN-nitroso-N-phosphonomethylglycine Dilithium salt ofN-nitroso-N-phosphonomethylglycine Trilithium salt ofN-nitroso-N-phosphonomethylglycine Barium salt ofN-nitroso-N-phosphonomethylglycine Monoammonium salt ofN-nitroso-N-phosphonomethylglvcine Mono-o-toluidine salt ofNnitroso-N-phosphonome- Monocyclohexylamine salt ofN-nitroso-N-phosphonomethylglycine 4 Monomorpholine salt ofN11iu'oso-N-phosphonomethylglycine Monoethanolamine salt ofN-nitroso-N-phosphonomethylglycine Monoethylamine salt ofN-nitroso-N-phosphonomethylglycine Monodimethylamine phonomethylglycincand aniline salts indicated on page 3 of application.

The compounds of the present invention show postemergent herbicidalactivity when applied at a rate of from 2 to 25 pounds per acre onspecies such as morn ingglory, Johnsongrass, barnyardgrass,lambsquarters and velvetleaf.

In employing the products of this invention as herbicides the activeingredients, that is, the product of this invention can be used alone orin combination with a material referred to in the art as an adjuvant inliquid or solid form. Herbicidal formulations are prepared by admixingthe ingredient with an adjuvant including diluents, extenders, carriersand conditioning agents to provide compositions in the form offinely-divided particulate solids, granules, pellets, solutions,dispersions or emulsions. Thus, the active ingredient can be used withan adjuvant such as a finely-divided particulate solid, a liquid oforganic origin, water, a wetting agent, dispersing agent, an emulsifyingagent or any suitable combination of these. The herbicidal formulationsusually contain from about 0.01 percent to about 99 percent by weight ofactive ingredient.

Typical finely-divided solid carriers and inert solid extenders whichcan be used with the active ingredients include, for example, the tales,natural and synthetic clays (e.g. kaolinites and attapulgite), pumice,silica, synthetic calcium and magnesium silicates, diatomaceous earth,quartz, Fullers earth, salt, sulfur, powdered cork, powdered wood,ground corn cobs, walnut flour, chalk, tobacco dust, charcoal, volcanicash, cottonseed hulls, wheat flour, soybean flour, tripoli and the like.Typical liquid diluents include for example; petroleum fractions such askerosene, hexane, xylene, benzene, Diesel Oil, toluene, acetone,ethylene dichloride, Stoddard solvent, alcohols such as propanol,glycols and the like.

Herbicidal formulations, particularly liquids and wettable particles,usually contain as a conditioning agent one or more surface-activeagents in amounts sufficient to render a given composition readilydispersible in water or in oil. By the term surface-active agent" it isunderstood that wetting agents, dispersing agents, suspending agents andemulsifying agents are included therein.

Specific surface-active agents which can be used in the herbicidalformulations of this invention are set out, for example, in Searle US.Pat. No. 2,426,417, Todd U.S. Pat. No. 2,655,447, Jones U.S. Pat. No.2,412,5IO and Lenher U.S. Pat. No. 2,139,276. A detailed list of suchagents is also set forth by .l. W. McCutcheon in an article in Soap andChemical Specialties, Vol. 3 I No 7, pages 50-61 see also McCutcheonarticle in Chemical Industries, November, 1947, page 81 I et seq.,entitled Synthetic Detergents", Detergents and Emulsifiers Up to Date(1960), by .l. W. McCutcheon, Inc, and Bulletin E-607 of the Bureau ofEntomology and Plant Quarantine of U.S.D.A. In general, less than 50parts by weight of the surface active agent is present per 100 parts byweight of phytotoxic formulation.

salt of N-nitroso-N-phos- Preferred wetting agents are alkyl benzene andalkyl naphthalene sulfonates, sulfated fatty alcohols, amines or acidamides, long chain acid esters of sodium isothi natc, este's of sodiumsu'f sutcinate,suiia ed or sub fonated fatty acid esters, petroleumsulfonates, sulfonoted vegetable oils, ditert ary acetylinic glycols,poly o vethyiene derivatives of alkylphenols (particularlyisooctylphenol and rcnylphenyl) and pclyoxyethylene derivatives of themono iigher fatty esters of hexitol ar-hydrides (e.g. sorbitan).Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodiumlignin sulfonates, polyme ic alkyl na ttbalene sulfonates, sodiumnaphthalene sulfonate, polyir ethylene bisnaphthalencsulfo'iate andsodium N--n .thyl-l*l-(lcng chain acid) tau rates.

Wettable powder formulations usually contain from about 5 to about 95parts by weight of active ingredient, from about 0.25 to parts by weightof wetting agent, from ab ut 0.25 to 25 parts by weight of dispersantand from 4.5 to about 94.5 parts by weight of inert sol d extender, allparts being by weight of the total formu ation. Where required, fromabout 0.1 to 2.0 parts by weight of the solid inert extender can bereplaced by a corrosion inh bitor or anti-foam ng r cfi.

Aqueous suspensions can be prepar v mixing to gether and grinding anaqueous slurry of waterinsoiuble active ingred ent in the presence ofdispersing agents to obtain a concentrated slurry of very finelydividedparticles. The resulting concentrated aqueous suspension ischaracterized by its extremely small particle s ze, so that when dilutedand sprayed, coverage is very uniform.

Dusts are dense finely-divided particulate formulations which areintended for application to the soil in dry form. Dusts arecharacterized by their free-flowing and rapid settling properties sothat they are not readiiy wind-borne to areas where they are of rovalue. Dusts contain primarily an ac ive ngredient and a dense,freellowing finely-divided particulate extender. However, theirperformance is sometimes aided by the inclusion of a wetting agent suchas those listed hereinbefore under wettable powder compositions andconvenience in manufacture frequently demands the inclusion of an inert,absorptive grinding aid. Suitable classes of grinding aids are naturalclays, diatomaceous earth and synthetic minerals derived from silica orsilicate. Preferred grinding aids include attapulgite clay, diat maceoussilica, synthetic fine silica and synthetic calcium and magnesiumsilicates.

The inert finely-divided solid extender for the dusts can be either ofvegetable or mineral origin. The solid extenders are characterized bypossessing relatively ow sur ce areas and are poor in liquid absorption.Suitable inert solid extenders for herb cidal dusts include n icaceoustales, pyrophyllite, dense kaolin clays, ground calcium phosphate rockand tobacco dust. The dusts usually contain from about 0.5 to 95 partsactive ingredient, to 50 parts grinding aid, 0 to parts wetting agentand 5 to 995 parts dense solid extender, all parts being by weight andbased on the total weight of the dust.

The wettable powders described above may also be used in the preparationof dusts. While such wettable powders could be used directly in dust.form, it is more advantageous to dilute them by blending with the densedust diluent. In this manner, dispersing agents, corrosion inhibitors,and antifoam agents may also be found as components of a dust.

Granules are physically stable particulate formulat ons comprisingactive ingredient adhering to or distributed through a basic matrix ofan inert, finelydivided particulate extender. In order to aid leachingof the active ingredient from the particulate, a surface active agentsuch as those listed hereinbefore under wettable powders can be presenin the composition. Natural clays, pyrn hyllites, illite and ermiculiteare examples of operable classes of particulate mineral extenders.Thepreferred extenders are the porous, absorptive, prefo med particlessuch as preformed and screened particulate attapulgite or heat expanded,par- .5 .etc vermiculite, and the finely-divided clays such Kaolin lays,hvdrated attapulgite or bentonitic clays. These extenders are sprayed orblended with the active ingredient to form the herbicidal formulations.

The mineral particles which are used in the herbicial formulationsusually have a size range of l0 to lOO mesh, but preferably such'that alarge majority of the particles have f om 14 to mesh with the optimumsine being from 20 to 40 mesh. Clay having substantially al particlesbetween 14 and mesh and at least about F30 percent between 20 and 40mesh is particularly preferred for use in the herbicidal formulations.The term mesh as used herein means U.S Sieve Series.

The granular herbicidal formulations generally contain from about 5parts to about 30 parts by weight of act ve ingredient per 100 parts. byweight of clay and O to about 5 parts by weight of surface active agentper H parts by weight of particulate clay. The preferred granularformulations contain from about l0 parts to about 25 parts by weight ofactive ingredient per parts by weight of clay.

The he b c dal comp sitions produced from the products cf this in ent oncan also contain other add tarnents, for fertilizers, phytotoxicants,other plant g ow-til: regularrts, pesticides and the like used asadjuvant or in combination with any of the above'described adjuvants.Chemicals useful in combination with the active ingredients: of thisinvention include for example, ureas, carbamates, acetamides, acetanilides, uracils, acetic acids, phenols, thiolcarbrnates, triazoles,benzoic acids, nitriles and the like.

What is claimed is:

l. A compound f the formula methyl or ethyl groups, with the provisothat at least one of M. M, and M is hydrogen when the others are otherthan an alkali metal or an alkaline earth metal.

2. A compound of claim 1 which is a monomonoalkyl ammonium, dialkylammonium or trialkyl ammonium salt.

1. A COMPOUND OF THE FORMULA
 2. A compound of claim 1 which is amonomonoalkyl ammonium, dialkyl ammonium or trialkyl ammonium salt.
 3. Acompound of claim 1 which is a monoanilinyl salt.
 4. A compound of claim1 which is a monosodium salt.